Aromatic amine derivatives

ABSTRACT

Novel aromatic amine derivatives of specific structure are useful intermediates for herbicides. The aromatic amine compounds have the structure shown by formula [I]: ##STR1## wherein Ar and A are as defined herein.

This is a division of application Ser. No. 07/151,594, filed Feb. 2, 1988 now U.S. Pat. No. 5,011,950.

BACKGROUND OF THE INVENTION

This invention relates to novel aromatic amine derivatives.

Wheat, corn, rice, and soybean plants are important crops. A variety of herbicides have been applied in order to increase crop yields. Prior art herbicides are not satisfactory in herbicidal activity and safety to growing crops. There is a need for a safe herbicide which can control weeds at a low level of application while giving no or little phytotoxity to growing crops.

During our research to produce a herbicide which is applicable in a small amount to kill weeds without phytotoxity to growing crops, we have discovered novel aromatic amine derivatives which are useful as intermediates for herbicides meeting the above requirements.

SUMMARY OF THE INVENTION

An object of the present invention is to provide novel aromatic amine derivatives which are useful as intermediates for herbicides.

According to the present invention, there is provided a novel aromatic amine derivative of the general formula [I]: ##STR2## wherein Ar is a radical selected from the group consisting of ##STR3## wherein R¹ to R¹⁵ and R¹⁷ to R³⁸ may be the same or different and are independently selected from the group consisting of hydrogen, lower alkyl radicals, and lower alkoxyl radicals, R¹⁶ is selected from the group consisting of hydrogen, lower alkyl radicals, lower alkoxyl radicals and hydroxyl, with the proviso that R² and R³, R⁶ and R⁷, R⁹ and R¹⁰, and R¹⁵, or R¹⁵ and R¹⁶ may, taken together, represent an alkylene chain, which may be substituted with a lower alkyl radical, to form a 5- or 6-membered ring with the carbon atoms to which they are attached, R¹¹ and R¹² may, taken together, represent an ethylene dioxyl radical, or R¹⁴ and R¹⁵ may, taken together, represent a dichloromethylene radical; and

A is a nitrogen atom or ##STR4## wherein X is selected from the group consisting of a hydrogen atom, a chlorine atom, a nitro radical, and a trifluoromethyl radical, when both R⁵ and R⁶ are methyl radicals and ##STR5## at least one of R⁷ and R⁸ does not represent hydrogen atom, when both R²⁵ and R²⁶ are methyl radicals and ##STR6## at least one of R²³ and R²⁴ does not represent hydrogen atom.

DETAILED DESCRIPTION OF THE INVENTION

The aromatic amine derivatives of the present invention have the general formula [I] as defined above.

Examples of the lower alkyl radicals represented by R¹ through R³⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Examples of the lower alkoxyl radicals represented by R¹ through R³⁸ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, etc.

Examples of the radicals represented by Ar are shown below. ##STR7##

Preferred examples of the aromatic amine derivatives of the present invention are shown in Tables 1 through 11. Particularly preferred examples of the aromatic amine derivatives of the present invention are compounds shown in Tables 1, 3, 4, 5, 6, 8, 9, 10 and 11.

                  TABLE 1                                                          ______________________________________                                          ##STR8##                                                                       Compound No.                                                                             R.sup.1                                                                                R.sup.2                                                                              R.sup.3                                                                               R.sup.4                                                                             ##STR9##                                  ______________________________________                                          1        CH.sub.3                                                                               H     H      H                                                                                    ##STR10##                                  2        CH.sub.3                                                                               H     H      H                                                                                    ##STR11##                                  3        CH.sub.3                                                                               H     CH.sub.3                                                                              CH.sub.3                                                                             ##STR12##                                  4        CH.sub.3                                                                               H     CH.sub.3                                                                              CH.sub.3                                                                             ##STR13##                                  5        H       H     H      H                                                                                    ##STR14##                                  6        C.sub.2 H.sub.5                                                                        H     H      H                                                                                    ##STR15##                                  7        C.sub.3 H.sub.7.sup.n                                                                  H     H      H                                                                                    ##STR16##                                  8        CH.sub.3                                                                               H     CH.sub.3                                                                              H                                                                                    ##STR17##                                  9        H       H     CH.sub.3                                                                              H                                                                                    ##STR18##                                 10        H       H     C.sub.2 H.sub.5                                                                       H                                                                                    ##STR19##                                 11        H       H     C.sub.3 H.sub.7.sup.i                                                                 H                                                                                    ##STR20##                                 12        H       H     C.sub.4 H.sub.9.sup.s                                                                 H                                                                                    ##STR21##                                 13        H       H     CH.sub.3                                                                              CH.sub.3                                                                             ##STR22##                                 14        H       H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR23##                                 15        H       H     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                      ##STR24##                                 16        CH.sub.3                                                                               H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR25##                                 17        CH.sub.3                                                                               H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR26##                                 18        CH.sub.3                                                                               H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR27##                                 19        CH.sub.3                                                                               H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR28##                                 20        CH.sub.3                                                                               H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      ##STR29##                                 21        C.sub.2 H.sub.5                                                                        H     CH.sub.3                                                                              CH.sub.3                                                                             ##STR30##                                 22        H       (CH.sub.2).sub.4                                                                          CH.sub.3                                                                             ##STR31##                                   ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                          ##STR32##                                                                      No.poundCom-                                                                         R.sup.5  R.sup.6  R.sup.7                                                                                R.sup.8                                                                             ##STR33##                                ______________________________________                                         23    CH.sub.3 H        H       H                                                                                    ##STR34##                                24    CH.sub.3 H        H       H                                                                                    ##STR35##                                25    H        H        CH.sub.3                                                                               H                                                                                    ##STR36##                                26    H        H        C.sub.2 H.sub.5                                                                        H                                                                                    ##STR37##                                27    H        H        C.sub.3 H.sub.7.sup.n                                                                  H                                                                                    ##STR38##                                28    H        H        C.sub.3 H.sub.7.sup.i                                                                  H                                                                                    ##STR39##                                29    C.sub.3 H.sub.7.sup.i                                                                   H        H       H                                                                                    ##STR40##                                30    OCH.sub.3                                                                               H        C.sub.2 H.sub.5                                                                        H                                                                                    ##STR41##                                31    CH.sub.3 H        CH.sub.3                                                                               H                                                                                    ##STR42##                                32    CH.sub.3 H        CH.sub.3                                                                               H                                                                                    ##STR43##                                33    CH.sub.3 CH.sub.3 H       H                                                                                    ##STR44##                                35    H        H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR45##                                36    OC.sub.2 H.sub.5                                                                        H        CH.sub.3                                                                               H                                                                                    ##STR46##                                37    OCH.sub.3                                                                               H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR47##                                38    OCH.sub.3                                                                               H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR48##                                39    OCH.sub.3                                                                               H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR49##                                40    OCH.sub.3                                                                               H        CH.sub.3                                                                               C.sub.2 H.sub.5                                                                      ##STR50##                                41    OCH.sub.3                                                                               H        C.sub.2 H.sub. 5                                                                       C.sub.2 H.sub.5                                                                      ##STR51##                                42    OCH.sub.3                                                                               H        C.sub.3 H.sub.7.sup.i                                                                  H                                                                                    ##STR52##                                43    OC.sub.2 H.sub.5                                                                        H        C.sub.2 H.sub.5                                                                        H                                                                                    ##STR53##                                44    OC.sub.2 H.sub.5                                                                        H        C.sub.3 H.sub.7.sup.i                                                                  H                                                                                    ##STR54##                                45    OC.sub.2 H.sub.5                                                                        H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR55##                                46    OC.sub.3 H.sub.7.sup.i                                                                  H        CH.sub.3                                                                               CH.sub.3                                                                             ##STR56##                                47    H        (CH.sub.2).sub.4                                                                              H                                                                                    ##STR57##                                  48    H                                                                                        ##STR58##     H                                                                                    ##STR59##                                  49    H                                                                                        ##STR60##     H                                                                                    ##STR61##                                  ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR62##                                                                      Compound No.                                                                                R.sup.9  R.sup.10                                                                               ##STR63##                                       ______________________________________                                         50           H        H                                                                                       ##STR64##                                       51           C.sub.2 H.sub.5                                                                         CH.sub.3                                                                                ##STR65##                                       52           CH.sub.3 CH.sub.3                                                                                ##STR66##                                       53           CH.sub.3 CH.sub.3                                                                                ##STR67##                                       54           OCH.sub.3                                                                               CH.sub.3                                                                                ##STR68##                                       55           OC.sub.2 H.sub.5                                                                        CH.sub.3                                                                                ##STR69##                                       56           OC.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         ##STR70##                                       57           OCH.sub.3                                                                               H                                                                                       ##STR71##                                       58           OC.sub.2 H.sub. 5                                                                       H                                                                                       ##STR72##                                       59           CH.sub.3 C.sub.3 H.sub.7.sup.i                                                                   ##STR73##                                       60           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         ##STR74##                                       61           (CH.sub.2).sub.4                                                                             ##STR75##                                           ______________________________________                                    

                                      TABLE 4                                      __________________________________________________________________________      ##STR76##                                                                      Compound No.                                                                           R.sup.11                                                                           R.sup.12                                                                           R.sup.13                                                                          R.sup.14                                                                          R.sup.15                                                                           R.sup.16                                                                            ##STR77##                                      __________________________________________________________________________      62     H   H   H  H  H   H                                                                                    ##STR78##                                       63     CH.sub.3                                                                           H   H  H  H   H                                                                                    ##STR79##                                       64     CH.sub.3                                                                           H   H  H  H   H                                                                                    ##STR80##                                       65     H   H   H  H  CH.sub.3                                                                           H                                                                                    ##STR81##                                       66     H   H   H  H  CH.sub.3                                                                           H                                                                                    ##STR82##                                       67     CH.sub.3                                                                           CH.sub.3                                                                           H  H  H   H                                                                                    ##STR83##                                       68     H   H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR84##                                       69     H   H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR85##                                       70     H   H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR86##                                       71     H   H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR87##                                       72     H   H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR88##                                       73     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           H                                                                                    ##STR89##                                       74     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           H                                                                                    ##STR90##                                       75     CH.sub.3                                                                           H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR91##                                       76     CH.sub.3                                                                           H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR92##                                       77     OCH.sub.3                                                                          H   H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR93##                                       78     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR94##                                       79     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR95##                                       80     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR96##                                       81     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR97##                                       82     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR98##                                       83     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     ##STR99##                                       84     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OC.sub.3 H.sub.7.sup.n                                                               ##STR100##                                      85     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OC.sub.3 H.sub.7 i                                                                   ##STR101##                                      86     OCH.sub.3                                                                          H   H  H  H   H                                                                                    ##STR102##                                      87     H   H   H  H  C.sub.2 H.sub.5                                                                    H                                                                                    ##STR103##                                      88     H   H   H  H  C.sub.3 H.sub.7.sup.i                                                              H                                                                                    ##STR104##                                      89     H   H   H  H  OCH.sub.3                                                                          H                                                                                    ##STR105##                                      90     H   H   H  H  OC.sub.2 H.sub.5                                                                   H                                                                                    ##STR106##                                      91     C.sub.2 H.sub.5                                                                    H   H  H  H   H                                                                                    ##STR107##                                      92     CH.sub.3                                                                           H   CH.sub.3                                                                          H  H   H                                                                                    ##STR108##                                      93     CH.sub.3                                                                           H   H  H  CH.sub.3                                                                           H                                                                                    ##STR109##                                      94     CH.sub.3                                                                           H   H  H  OCH.sub.3                                                                          H                                                                                    ##STR110##                                      95     CH.sub.3                                                                           H   H  H  OC.sub.2 H.sub.5                                                                   H                                                                                    ##STR111##                                      96     OCH.sub.3                                                                          H   H  H  CH.sub.3                                                                           H                                                                                    ##STR112##                                      97     OCH.sub.3                                                                          H   H  H  C.sub.2 H.sub.5                                                                    H                                                                                    ##STR113##                                     98      H   H   CH.sub.3                                                                          H  CH.sub.3                                                                           H                                                                                    ##STR114##                                     99      H   H   CH.sub.3                                                                          H  C.sub.2 H.sub.5                                                                    H                                                                                    ##STR115##                                     100     H   H   H  H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      ##STR116##                                     101     H   H   H  H  CH.sub.3                                                                           C.sub.3 H.sub.7.sup.n                                                                ##STR117##                                     102     H   H   H  H  CH.sub.3                                                                           C.sub.3 H.sub.7.sup.i                                                                ##STR118##                                     103     H   H   H  H  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      ##STR119##                                     104     H   H   H  H  C.sub.2 H.sub.5                                                                    C.sub.3 H.sub.7.sup.n                                                                ##STR120##                                     105     H   H   H  H  (CH.sub.2).sub.5                                                                         ##STR121##                                     106     H   H   H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR122##                                     107     H   H   H  H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                     ##STR123##                                     108     H   H   H  H  CH.sub.3                                                                           OC.sub.3 H.sub.7.sup.i                                                               ##STR124##                                     109     H   H   H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            ##STR125##                                     110     CH.sub.3                                                                           H   H  H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR126##                                     111     CH.sub.3                                                                           H   H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                                                            ##STR127##                                     112     OCH.sub.3                                                                          H   CH.sub.3                                                                          H  CH.sub.3                                                                           H                                                                                    ##STR128##                                     113     H   H   CH.sub.3                                                                          H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR129##                                     114     H   H   CH.sub.3                                                                          H  CH.sub.3                                                                           OCH.sub.3                                                                            ##STR130##                                     115     OCH.sub.3                                                                          H   H  H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      ##STR131##                                     116     OCH.sub.3                                                                          H   H  H  CH.sub.3                                                                           C.sub.3 H.sub.7.sup.i                                                                ##STR132##                                     117     OCH.sub.3                                                                          H   H  H  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      ##STR133##                                     118     OCH.sub.3                                                                          H   H  H  C.sub.2 H.sub.5                                                                    C.sub.3 H.sub.7.sup.n                                                                ##STR134##                                     119     O(CH.sub.2).sub.2 O                                                                    H  H  CH.sub.3                                                                           H                                                                                    ##STR135##                                     120     O(CH.sub.2).sub.2 O                                                                    H  H  C.sub.2 H.sub.5                                                                    H                                                                                    ##STR136##                                     121     O(CH.sub.2).sub.2 O                                                                    H  H  C.sub.3 H.sub.7.sup.i                                                              H                                                                                    ##STR137##                                     122     O(CH.sub.2).sub.2 O                                                                    CH.sub.3                                                                          H  CH.sub.3                                                                           H                                                                                    ##STR138##                                     123     O(CH.sub.2).sub.2 O                                                                    H  H  CH.sub.3                                                                           CH.sub.3                                                                             ##STR139##                                     124     O(CH.sub.2).sub.2 O                                                                    H  H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      ##STR140##                                     125     O(CH.sub.2).sub.2 O)                                                                   H  H  CH.sub.3                                                                           C.sub.3 H.sub.7.sup.i                                                                ##STR141##                                     126     O(CH.sub.2).sub.2 O                                                                    H  H  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                      ##STR142##                                     127     O(CH.sub.2).sub.2 O                                                                    H  H  C.sub.2 H.sub.5                                                                    C.sub.3 H.sub.7.sup.n                                                                ##STR143##                                     128     CH.sub.3                                                                           CH.sub.3                                                                           H  CCl.sub.2                                                                             CH.sub.3                                                                             ##STR144##                                     129                                                                                     ##STR145##                                                                                            ##STR146##                                     130                                                                                     ##STR147##                                                                                            ##STR148##                                     131     CH.sub.3                                                                           CH.sub.3                                                                           H  H  CH.sub.3                                                                           OH                                                                                   ##STR149##                                     __________________________________________________________________________

                  TABLE 5                                                          ______________________________________                                          ##STR150##                                                                     Compound No.                                                                             R.sup.17                                                                              R.sup.18                                                                               R.sup.19                                                                             R.sup.20                                                                             ##STR151##                               ______________________________________                                         132       CH.sub.3                                                                              H       H     H                                                                                     ##STR152##                               133       CH.sub.3                                                                              H       H     H                                                                                     ##STR153##                               134       CH.sub.3                                                                              CH.sub.3                                                                               H     H                                                                                     ##STR154##                               135       CH.sub.3                                                                              CH.sub.3                                                                               H     H                                                                                     ##STR155##                               136       H      H       CH.sub.3                                                                             CH.sub.3                                                                              ##STR156##                               137       CH.sub.3                                                                              OCH.sub.3                                                                              H     H                                                                                     ##STR157##                               ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                          ##STR158##                                                                     Compound No.                                                                               R.sup.21   R.sup.22                                                                               ##STR159##                                     ______________________________________                                         138         C.sub.3 H.sub.7.sup.i                                                                     H                                                                                       ##STR160##                                     139         C.sub.4 H.sub.9.sup.i                                                                     H                                                                                       ##STR161##                                     140         H          C.sub.2 H.sub.5                                                                         ##STR162##                                     141         H          C.sub.3 H.sub.7.sup.n                                                                   ##STR163##                                     142         H          C.sub.3 H.sub.7.sup.i                                                                   ##STR164##                                     ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                          ##STR165##                                                                     Compound No.                                                                             R.sup.23                                                                               R.sup.24                                                                              R.sup.25                                                                             R.sup.26                                                                             ##STR166##                               ______________________________________                                         143       H       H      CH.sub.3                                                                             H                                                                                     ##STR167##                               144       H       H      CH.sub.3                                                                             H                                                                                     ##STR168##                               ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                          ##STR169##                                                                     Compound No.                                                                               R.sup.27                                                                              R.sup.28                                                                                R.sup.29                                                                            ##STR170##                                   ______________________________________                                         146         H      CH.sub.3 CH.sub.3                                                                             ##STR171##                                   ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                          ##STR172##                                                                     Compound No.                                                                               R.sup.30  R.sup.31                                                                              ##STR173##                                       ______________________________________                                         147         CH.sub.3  CH.sub.3                                                                               ##STR174##                                       ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                          ##STR175##                                                                     Compound No.                                                                               R.sup.32                                                                              R.sup.33                                                                                R.sup.34                                                                            ##STR176##                                   ______________________________________                                         148         CH.sub.3                                                                              CH.sub.3 CH.sub.3                                                                             ##STR177##                                   149         CH.sub.3                                                                              CH.sub.3 C.sub.2 H.sub.5                                                                      ##STR178##                                   ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                          ##STR179##                                                                     Compound No.                                                                             R.sup.35                                                                              R.sup.36                                                                               R.sup.37                                                                             R.sup.38                                                                             ##STR180##                               ______________________________________                                         150       H      H       CH.sub.3                                                                             CH.sub.3                                                                              ##STR181##                               151       H      H       OCH.sub.3                                                                            CH.sub.3                                                                              ##STR182##                               152       H      CH.sub.3                                                                               OCH.sub.3                                                                            CH.sub.3                                                                              ##STR183##                               ______________________________________                                    

PREPARATION

The aromatic amine derivatives of the present invention may be prepared through a series of reactions as shown by the following formulae (1) and (2). ##STR184## The reaction of formula (1) may be carried out by agitating the reagents in an aromatic hydrocarbon such as benzene, toluene, and xylene, an aprotic polar solvent such as N,N-dimethylformamide and 1-methyl-2-pyrrolidone, or a mixture thereof in the presence of a base such as NaOH, KOH, Na₂ CO₃, K₂ CO₃, NaH at a temperature of from 20° C. to 150° C. The reaction of formula (2) may proceed in a solvent inert to the reaction, for example, benzene, toluene, xylene, methanol, ethanol and ethyl acetate, in the presence of an ordinary reducing catalyst such as Raney nickel catalysts and palladium-carrying carbon under atmospheric pressure to a hydrogen pressure of 20 g/cm² at a temperature of from 20° C. to 100° C.

Among the compounds of general formula [II], those compounds represented by general formula [II-1]: ##STR185## wherein R¹¹, R¹², R¹³ and A are as defined above, R¹⁶⁻¹ is a lower alkoxy or hydroxyl radical can be produced not only by the reaction of formula (1), but also by a series of reactions as shown by formulae (3) and (4). ##STR186## The reaction of formula (3) may proceed under the same conditions as described for the reaction of formula (1). The reaction of formula (4) may be carried out without solvent or in an inert solvent such as acetone, dioxane, benzene and toluene in the presence of an acid catalyst such as HCl, H₂ SO₄ and Amberlist-15 by heating to a temperature of from 40° C. to 120° C.

Among the compounds of general formula [II], those compounds represented by general formula [II-2]: ##STR187## wherein R¹¹, R¹², and A are as defined above can be produced not only by the reaction of formula (1), but also by reaction as shown by formula (5).

    [III]+:CCl.sub.2 →[II-2]                            (5)

The reaction of formula (5) can be carried out by agitating a mixture of compound [III], chloroform, and NaOH or KOH without solvent or in an aqueous medium in the presence of a quaternary ammonium salt such as benzyltrimethyl ammonium chloride.

At the end of reaction, the end product can be recovered by a conventional method as shown in the following examples.

For typical ones of compounds Ar-OH used in the above preparation procedure, their typical synthesis is exemplified in Table 12 of Japanese Patent Application No. 61-177858 (WO 87/00840). Those compounds which are not exemplified in this Application may also be synthesized by a similar procedure.

EXAMPLES

Examples of the aromatic amine derivatives of the present invention are presented below by way of illustration and not by way of limitation.

REFERENCE 1 Synthesis of 2-(3-methyl-2,3-dihydro-6-benzofuryloxy)-5-nitropyridine

A 50-ml two-necked round-bottomed flask equipped with a dropping funnel was charged with 0.64 grams of sodium hydride and washed twice with n-hexane. To the flask were added dropwise 2.0 grams of 3-methyl-2,3-dihydro-6-benzofuranol and 10 ml of dimethylformamide at room temperature. After evolution of hydrogen ceased, 2.1 grams of 2-chloro-5-nitropyridine in 10 ml of dimethylformamide was added dropwise. The mixture was agitated for 3 hours at room temperature. After water was added to the reaction mixture, the product was extracted with ethyl acetate, washed with water, and then dried over anhydrous magnesium sulfate. The extracting solvent was distilled off to leave a residue, which was purified by chromatography through a silica gel column using a 4/1 n-hexane/ethyl acetate mixture, obtaining 3.0 grams of brown crystals (yield 83%).

Melting point 99.0°-99.5° C.

IR spectrum (KBr disk; cm⁻¹): 3120, 3020, 2950, 1605, 1585, 1515, 1420, 1340, 1240, 998

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR188##

REFERENCE 2 Synthesis of 4-(3-methyl-2,3-dihydro-6-benzofuryloxy)-nitrobenzene

A 50-ml two-necked round-bottomed flask equipped with a Dean-Stark apparatus and a condenser was charged with 2.0 grams of 3-methyl-2,3-dihydro-6-benzofuranol, 2.1 grams of 4-chloronitrobenzene, 1.1 grams of 85% potassium hydroxide, 5.0 ml of toluene, and 5.0 ml of dimethylformamide. The mixture was agitated for 21/2 hours at 140° C. while removing water formed. The reaction mixture was allowed to cool and then combined with water. The product was extracted with ethyl acetate, washed with water, and then dried over anhydrous magnesium sulfate. The extracting solvent was distilled off to leave a residue which was purified by chromatography through a silica gel column using a 4/1 n-hexane/ethyl acetate mixture, obtaining 3.1 grams of pale green crystals (yield 86%).

Melting point 90°-91° C.

IR spectrum (KBr disk; cm⁻¹): 3050, 2960, 1603, 1575, 1420, 1350, 1271, 1237, 1142, 997

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR189##

EXAMPLE 1 Compound No. 1: 2-(3-methyl-2,3-dihydro-6-benzofuryloxy)-5-aminopyridine

In 20 ml of ethyl acetate was dissolved 2.0 grams of 2-(3-methyl-2,3-dihydro-6-benzofuryloxy)-5-nitropyridine. The solution was catalytically reduced in the presence of 0.2 grams of 5% palladium-carrying carbon at room temperature. After absorption of hydrogen ceased, the catalyst was filtered off and the filtrate was concentrated. The concentrate was purified by chromatography through a silica gel column using ethyl acetate solvent, obtaining 1.7 grams of the end product in the form of colorless liquid (yield 97%).

Mass spectrum: m/z 242 (molecular ion peak)

IR spectrum (neat; cm⁻¹): 3400, 3050, 2950, 1602, 1357, 1271, 1235, 1130

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR190##

EXAMPLE 2 Compound No. 2: 4-(3-methyl-2,3-dihydro-6-benzofuryloxy)-aniline

The procedure of Example 1 was repeated except that the 2-(3-methyl-2,3-dihydro-6-benzofuryloxy)-5-nitropyridine was replaced by 4-(3-methyl-2,3-dihydro-6-benzofuryloxy)nitrobenzene. The reaction mixture was worked up in the same manner as in Example 1, obtaining the end product in the form of brown liquid (yield 98%).

Mass spectrum: m/z 241 (molecular ion peak)

IR spectrum (neat; cm⁻¹): 3350, 3050, 2970, 1601, 1357, 1270, 1236, 1132

¹ H-NMR spectrum (CDCl₃ solution; ppm) ##STR191##

Compound Nos. 3 to 152 were synthesized by the same procedure as in Example 1. The results are summarized in Tabel 12. The yield was at least 95% for all the compounds.

                                      TABLE 12                                     __________________________________________________________________________     Compound                                                                       No.     As-produced  Spectral analysis                                         __________________________________________________________________________     3       viscous liquid                                                                              NMR: 1.20(3H, d, J=8.1), 1.28(3H, s), 1.47(3H, s),                             3.07(1H, q, J=8.1),                                                            3.35(2H, brs), 6.24˜8.00(6H, m).                    4       viscous liquid                                                                              NMR: 1.19(3H, d, J=9.0), 1.45(3H, s), 3.10(1H, q,                              J=9.0), 3.38(2H, brs),                                                         6.28˜7.10(7H, m).                                   5       viscous liquid                                                                              NMR: 3.15(2H, t, J=7.2), 3.40(2H, brs), 4.60(2H, t,                            J=7.2), 6.20˜7.40(7H, m).                           6       viscous liquid                                                                              NMR: 0.96(3H, t, J=7.2), 1.70(2H, q, J=7.2),                                   3.30(1H, m), 3.42(2H, brs),                                                    4.24(1H, t, J=9.0), 4.65(1H, t, J=9.0),                                        6.30˜7.50(7H, m).                                   7       viscous liquid                                                                              IR: 3350(ν.sub.NH), 3100, 2980, 1610, 1270,                                 1230.                                                     8       viscous liquid                                                         9       viscous liquid                                                                              NMR: 1.46(3H, d, J=7.2), 2.74(1H, dd, J=8.0, 15.0),                            3.27(1H, dd, J=8.0, 15.0),                                                     3.52(2H, brs), 4.94(1H, m), 6.28˜7.42(7H, m).       10      viscous liquid                                                                              NMR: 1.04(3H, t, J=7.2), 1.76(2H, m), 2.78(1H, dd,                             J=8.0, 15.0),                                                                  3.22(1H, dd, J=8.0, 15.0), 3.55(2H, brs),                                      6.20˜7.10(7H, m).                                   11      viscous liquid                                                                              NMR: 0.98(3H, d, J=7.2), 1.06(3H, d, J=7.2),                                   1.89(1H, m),                                                                   2.85(1H, dd, J=8.0, 15.0), 3.14(1H, dd, J=8.0,                                 15.0), 3.48(2H, brs),                                                          4.54(1H, m), 6.35˜7.20(7H, m).                      12      viscous liquid                                                                              NMR: 0.93(3H, t, J=7.2), 1.00(3H, d, J=7.2),                                   1.61(3H, m), 2.70˜3.30(2H, m),                                           3.42(2H, brs), 6.35˜7.20(7H, m).                    13      m.p. 86˜87° C.                                            14      viscous liquid                                                                              NMR: 0.95(3H, t, J=7.0), 1.40(3H, s), 1.74(2H, q,                              J=7.0), 2.95(2H, s), 3.42(2H, brs),                                            6.30˜7.40(7H, m).                                   15      viscous liquid                                                                              NMR: 0.91(6H, t, J=7.0), 1.70(4H, q, J=7.0),                                   2.95(2H, s), 3.46(2H, brs),                                                    6.30˜7.20(7H, m).                                   16      viscous liquid                                                                              NMR: 0.90(3H, t, J=7.2), 1.14(3H, d, J=6.3),                                   1.17(3H, s), 1.70(2H, q, J=7.2),                                               3.08(1H, q, J=6.3), 3.30(2H, brs),                                             6.25˜7.60(6H, m).                                   17      viscous liquid                                                                              NMR: 0.98(3H, t, J=7.2), 1.20(3H, d, J=6.3),                                   1.24(3H, s), 1.75(2H, q, J=7.2),                                               3.10(1H, q, J=6.3), 3.45(2H, brs),                                             6.30˜7.20(7H, m).                                   18      viscous liquid                                                                              NMR: 0.99(3H, t, J=7.2), 1.22(3H, d, J=6.3),                                   1.24(3H, s), 1.78(2H, q, J=7.2),                                               3.18(1H, d, J=6.3), 3.52(2H, brs),                                             6.28˜7.50(7H, m).                                   19      viscous liquid                                                                              IR: 3400, 3320(μ.sub.NH).                              20      viscous liquid                                                                              IR: 3410, 3310(μ.sub.NH).                              21      viscous liquid                                                                              NMR: 1.26(3H, t, J=7.2), 1.34(3H, s), 1.46(3H, s),                             1.63(2H, m), 2.84(1H, t, J=9.0),                                               3.36(2H, brs), 6.18˜7.16(7H, m).                    22      viscous liquid                                                         23      viscous liquid                                                                              NMR: 1.49(3H, d, J=6.3), 2.80˜3.40(2H, m),                               3.55(2H, brs), 4.90(1H, m),                                                    6.24˜7.62(6H, m).                                   24      m.p. 101˜102° C.                                          25      viscous liquid                                                                              NMR: 1.29(3H, d, J=6.9), 3.52(3H, m), 4.12(1H, t,                              J=9.0), 4.71(1H, t, J=9.0),                                                    6.20˜7.15(7H, m).                                   26      viscous liquid                                                                              NMR: 0.94(3H, t, J=7.2), 1.70(2H, q, J=7.2),                                   3.44(3H, m), 4.21(1H, dd, J=7.2, 9.0),                                         4.63(1H, t, J=9.0), 6.15˜7.50(7H, m).               27      viscous liquid                                                                              NMR: 0.96(3H, t, J=7.0), 1.24˜1.78(4H, m),                               3.10(1H, m), 3.42(2H, brs),                                                    4.21(1H, dd, J=7.2, 9.0), 4.66(1H, t, J=9.0),                                  6.34˜7.26(7H, m).                                   28      viscous liquid                                                         29      viscous liquid                                                         30      viscous liquid                                                                              NMR: 0.97(3H, t, J=7.2), 1.36˜1.90(2H, m),                               2.90˜3.20(1H, m), 3.50(2H, brs),                                         3.53(3H, s), 5.26(3H, d, J=2.7), 6.52˜7.36(7H,                           m).                                                       31      viscous liquid                                                         32      m.p. 89.5˜90.5° C.                                        33      viscous liquid                                                         35      m.p. 94.5˜95.5° C.                                        36      viscous liquid                                                         37      viscous liquid                                                                              NMR: 1.27(3H, s), 1.29(3H, s), 3.30(2H, brs),                                  3.56(3H, s), 5.13(1H, s),                                                      6.50˜7.80(6H, m).                                   38      viscous liquid                                                                              NMR: 1.25(3H, s), 1.28(3H, s), 3.30(2H, brs),                                  3.56(3H, s), 5.11(1H, s),                                                      6.48˜7.00(7H, m).                                   39      viscous liquid                                                                              NMR: 1.24(3H, s), 1.28(3H, s), 3.34(3H, s), 3.60(2H,                           brs), 5.10(1H, s),                                                             6.40˜6.90(6H, m).                                   40      viscous liquid                                                         41      viscous liquid                                                         42      viscous liquid                                                                              NMR: 0.90(3H, d, J=6.4), 0.94(3H, d, J=6.4),                                   1.72˜2.00(1H, m), 2.50˜2.70(1H, m),                                3.34(2H, brs), 5.32(3H, d, J=2.1),                                             6.40˜7.20(7H, m).                                   43      viscous liquid                                                                              NMR: 0.96(3H, t, J=7.7), 1.23(3H, t, J=7.1),                                   1.40˜1.84(2H, m), 3.01˜3.16(1H, m),                                3.52˜4.00(4H, m), 5.38(1H, d, J=2.1),                                    6.41˜7.18(7H, m).                                   44      viscous liquid                                                                              NMR: 0.88(3H, d, J=6.4), 0.92(3H, d, J=6.4),                                   1.24(3H, t, J=7.1), 1.80˜2.12(1H, m),                                    3.02˜3.12(1H, m), 3.52˜4.06(4H, m),                                5.44(1H, d, J=1.5), 6.40˜7.18(4H, m).               45      viscous liquid                                                         46      viscous liquid                                                         47      viscous liquid                                                                              NMR: 1.30˜2.16(8H, m), 3.13˜3.36(1H, m),                           3.52(2H, brs), 4.64˜4.88(1H, m),                                         6.32˜7.41(7H, m).                                   48      viscous liquid                                                                              IR: 3400(ν.sub.NH), 3040, 2960, 1570, 1270,                                 1120.                                                     49      viscous liquid                                                         50      viscous liquid                                                                              NMR: 3.48(2H, brs), 5.89(2H, s), 6.20˜6.90(7H,                           m)                                                        51      viscous liquid                                                                              NMR: 1.01(3H, t, J=7.2), 1.61(3H, s), 1.95(2H, q,                              J=7.2), 3.40(2H, brs),                                                         6.20˜7.10(7H, m).                                   52      viscous liquid                                                         53      viscous liquid                                                                              NMR: 1.68(6H, s), 3.45(2H, brs), 6.20˜7.10(7H,                           m).                                                       54      viscous liquid                                                                              NMR: 1.78(3H, s), 3.31(3H, s), 3.55(2H, brs),                                  6.30˜7.00(7H, m).                                   55      viscous liquid                                                                              NMR: 1.21(3H, t, J=7.2), 1.80(3H, s), 3.32(2H, brs),                           3.61(2H, q, J=7.2),                                                            6.30˜7.08(7H, m).                                   56      viscous liquid                                                                              NMR: 1.02(3H, t, J=7.2), 1.21(3H, t, J=7.2),                                   2.06(2H, q, J=7.2),                                                            3.56(2H, q, J=7.2), 3.60(2H, brs),                                             6.30˜7.00(7H, m).                                   57      viscous liquid                                                         58      viscous liquid                                                         59      viscous liquid                                                                              IR: 3400(ν.sub.NH), 3060, 2970, 1603.                  60      viscous liquid                                                         61      viscous liquid                                                                              IR: 3420(ν.sub.NH), 3040, 2970, 1603, 1275.            62      viscous liquid                                                         63      viscous liquid                                                                              IR: 3400(ν.sub.NH), 3060, 2955, 1605, 1275,                                 1238.                                                     64      m.p. 109˜110° C.                                          65      viscous liquid                                                                              NMR: 1.38(3H, d, J=7.2), 1.60˜2.00(2H, m),                               2.64˜2.94(2H, m), 3.37(2H, m),                                           6.40˜7.80(6H, m).                                   66      viscous liquid                                                                              NMR: 1.38(3H, d, J=9.0), 1.80(2H, m), 2.72(2H, m),                             2.64(2H, brs), 4.16(1H, m),                                                    6.40˜7.80(6H, m).                                   67      m.p. 115.5˜116.5° C.                                      68      m.p. 93˜94° C.                                                                 NMR: 1.30(6H, s), 1.76(2H, t, J=7.2), 2.72(2H, t,                              J=7.2), 3.38(2H, brs),                                                         6.40˜7.80(6H, m).                                   69      viscous liquid                                                                              NMR: 1.30(6H, s), 1.77(2H, t, J=7.2), 2.72(2H, t,                              J=7.2), 3.44(2H, brs),                                                         6.20˜7.18(7H, m).                                   70      viscous liquid                                                                              NMR: 1.32(6H, s), 1.78(2H, t, J=7.2), 2.72(2H, t,                              J=7.2), 3.64(2H, brs),                                                         6.20˜7.10(6H, m).                                   71      viscous liquid                                                                              IR: 3420(ν.sub.NH), 3040, 2970, 1605, 1535,                                 1370.                                                     72      viscous liquid                                                         73      viscous liquid                                                                              NMR: 1.29(3H, s), 1.32(3H, d, J=7.2), 1.62(1H, s),                             1.68(1H, s), 3.28(2H, brs),                                                    4.16(1H, q, J=7.2), 6.40˜7.80(6H, m).               74      viscous liquid                                                         75      viscous liquid                                                                              IR: 3380(μ.sub.NH), 3180, 3040, 2960, 1605,                                 1275.                                                     76      viscous liquid                                                                              IR: 3410(μ.sub.NH), 3060, 2970, 1610, 1270, 1235,                           1140.                                                     77      viscous liquid                                                                              NMR: 1.32(3H, s), 1.41(3H, s), 1.99(1H, d, J=7.2),                             2.03(1H, d, J=7.2), 3.44(3H, s),                                               3.50(2H, brs), 4.38(1H, t, J=7.2),                                             6.20˜7.40(7H, m).                                   78      m.p. 104.5˜105.5° C.                                      79      viscous liquid                                                                              NMR: 1.26(3H, s), 1.41(3H, s), 1.49(3H, s), 1.81(1H,                           d, J=14.0), 1.95(1H, d, J=14.0),                                               2.65(2H, brs), 3.23(3H, s), 6.40˜7.30(7H, m).       80      viscous liquid                                                                              NMR: 1.25(3H, s), 1.41(3H, s), 1.48(3H, s), 1.80(1H,                           d, J=14.4), 2.02(1H, d, J=14.4),                                               3.21(3H, s), 3.64(2H, brs), 6.20˜7.32(7H, m).       81      viscous liquid                                                                              IR: 3410(ν.sub.NH), 3330(ν.sub.NH), 1610,                                1524, 1470, 1350, 1265, 1230.                             82      viscous liquid                                                         83      viscous liquid                                                                              NMR: 1.00(3H, t, J=7.2), 1.26(3H, s), 1.44(3H, s),                             1.50(3H, s), 1.88(1H, d, J=14.0),                                              1.95(1H, d, J=14.0), 3.35(2H, brs), 3.55(2H, q,                                J=7.2), 6.32˜7.30(7H, m).                           84      viscous liquid                                                                              NMR: 0.72(3H, t, J=7.2), 1.20˜1.60(2H, m),                               1.28(3H, s), 1.46(3H, s), 1.54(3H, s),                                         1.84(1H, d, J=13.5), 2.05(1H, d, J=13.5), 3.47(4H,                             m), 6.20˜7.20(7H, m).                               85      viscous liquid                                                                              NMR: 0.84, 1.11(total 6H, d, J=7.2), 1.25(3H, s),                              1.45(3H, s), 1.51(3H, s),                                                      1.74(1H, d, J=13.5), 1.99(1H, d, J=13.5), 3.56(2H,                             brs), 4.12(1H, m),                                                             6.30˜7.26(7H, m).                                   86      viscous liquid                                                                              NMR: 1.82˜2.20(2H, m), 3.43(3H, s), 3.48(2H,                             brs), 4.10˜4.36(3H, m),                                                  6.30˜7.35(7H, m).                                   87      viscous liquid                                                                              NMR: 1.00(3H, t, J=7.2), 1.40˜2.16(4H, m),                               2.50˜3.00(2H, m), 3.50(2H, brs),                                         3.70˜4.04(1H, m), 6.20˜7.33(7H, m).           88      viscous liquid                                                         89      viscous liquid                                                                              NMR: 1.90(2H, m), 2.56(2H, m), 3.40(3H, s), 3.52(2H,                           brs), 5.01(1H, t, J=1.8),                                                      6.18˜7.31(7H, m).                                   90      viscous liquid                                                         91      viscous liquid                                                                              NMR: 1.00(3H, t, J=7.2), 1.80(4H, m), 2.60(1H, m),                             3.48(2H, brs), 4.16(2H, t, J=5.4),                                             6.10˜7.15(7H, m).                                   92      viscous liquid                                                                              NMR: 0.97(3H, d, J=7.2), 1.18(3H, d, J=7.2),                                   2.00˜2.10(1H, m), 2.72˜3.04(1H, m),                                3.48(2H, brs), 3.78˜4.20(2H, m),                                         6.30˜7.10(7H, m).                                   93      viscous liquid                                                         94      viscous liquid                                                                              NMR: 1.30, 1.35(total 3H, d, J=7.2),                                           1.60˜2.28(2H, m), 2.94(1H, m),                                           3.47, 3.51(total 3H, s), 3.49(2H, brs),                                        6.30˜7.42(7H, m).                                   95      viscous liquid                                                                              NMR: 1.00˜1.50(6H, m), 1.60˜2.28(2H, m),                           3.08(1H, m), 3.24˜4.08(4H, m),                                           5.20(1H, dd, J=3.6, 7.2), 6.32˜7.46(7H, m).         96      viscous liquid                                                                              NMR: 1.40(3H, d, J=7.2), 1.62˜2.44(2H, m),                               3.44(3H, s), 3.54(2H, brs), 4.20(1H, m),                                       4.56(1H, dd, J=6.3, 10.8), 6.21˜7.32(7H, m).        97      viscous liquid                                                         98      viscous liquid                                                                              NMR: 0.96(3H, d, J=7.2), 1.26(3H, d, J=7.2),                                   2.00˜3.08(3H, m), 3.48(2H, m),                                           4.08˜4.18(1H, m), 6.33˜7.20(7H, m).           99      viscous liquid                                                                              NMR: 0.82˜1.12(6H, m), 1.20˜1.81(3H, m),                           2.20˜2.80(2H, m), 3.48(2H, brs),                                         4.10(1H, m), 6.24˜7.26(7H, m).                      100     viscous liquid                                                         101     viscous liquid                                                                              IR: 3420(ν.sub.NH), 3070, 2940, 1570, 1275,                                 1238.                                                     102     viscous liquid                                                                              IR: 3420(ν.sub.NH), 3050, 2955, 1610, 1570, 1575,                           1240.                                                     103     viscous liquid                                                         104     m.p. 85˜86° C.                                                                 NMR: 0.89(6H, t, J=7.2), 1.25˜1.67(6H, m),                               1.78(2H, t, J=7.2), 2.68(2H, t, J=7.2),                                        3.48(2H, brs), 6.32˜7.22(7H, m).                    105     viscous liquid                                                         106     viscous liquid                                                                              NMR: 1.55(3H, s), 1.64˜2.24(2H, m),                                      2.36˜3.04(2H, m), 3.28(2H, brs), 3.30(3H, s),                            6.36˜7.10(7H, m).                                   107     viscous liquid                                                                              NMR: 1.04(3H, t, J=7.2), 1.58(3H, s),                                          1.70˜2.28(2H, m), 2.60˜3.24(2H, m),                                3.48(2H, brs), 3.62(2H, q, J=7.2),                                             6.36˜7.40(7H, m).                                   108     viscous liquid                                                                              NMR: 0.85(3H, t, J=7.2), 1.14(3H, t, J=7.2),                                   1.54(3H, s), 1.66˜2.24(2H, m),                                           2.40˜2.80(2H, m), 3.49(2H, brs), 4.22(1H, m),                            6.26˜7.38(7H, m).                                   109     viscous liquid                                                                              NMR: 0.95(3H, t, J=7.2), 1.50˜2.20(4H, m),                               2.40˜3.00(2H, m), 3.24(3H, s),                                           3.38(2H, brs), 6.36˜7.08(7H, m).                    110     viscous liquid                                                         111     viscous liquid                                                         112     viscous liquid                                                                              NMR: 1.08(3H, d, J=7.2), 1.40(3H, d, J=7.2),                                   1.60˜2.00(1H, m), 3.31(3H, s),                                           3.51(2H, brs), 3.80˜4.36(2H, m),                                         6.20˜7.40(7H, m).                                   113     viscous liquid                                                                              NMR: 0.99(3H, d, J=7.2), 1.14(3H, s), 1.35(3H, s),                             1.62˜2.10(1H, m),                                                        2.30˜2.88(2H, m), 3.47(2H, brs),                                         6.30˜7.12(7H, m).                                   114     viscous liquid                                                                              NMR: 1.08(3H, d, J=7.2), 1.49(3H, s), 1.98(1H, m),                             2.46˜2.76(2H, m), 3.23(3H, s),                                           3.42(2H, brs), 6.20˜7.12(7H, m).                    115     viscous liquid                                                                              NMR: 0.94(3H, t, J=7.2), 1.25 and 1.36(total 3H, s),                           1.50˜1.76(2H, m),                                                        1.81˜2.12(2H, m), 3.44 and 3.46(total 3H, s),                            3.54(2H, brs), 4.41(1H, brs),                                                  6.24˜7.30(7H, m).                                   116     viscous liquid                                                         117     viscous liquid                                                                              NMR: 0.89(6H, t, J=7.2), 1.50˜2.10(6H, m),                               3.44(3H, s), 3.50(2H, brs),                                                    4.37(1H, t, J=6.3), 6.20˜7.40(7H, m).               118     viscous liquid                                                                              NMR: 0.90(6H, t, J=7.2), 1.10˜2.20(8H, m),                               3.46(3H, s), 3.52(2H, brs),                                                    4.38(1H, t, J=7.2), 6.30˜7.40(7H, m).               119     viscous liquid                                                         120     viscous liquid                                                                              NMR: 1.04(3H, t, J=7.2), 1.52˜2.14(4H, m),                               3.42(3H, brs), 3.92˜4.40(5H, m),                                         6.20˜7.20(7H, m).                                   121     viscous liquid                                                                              NMR: 1.00(6H, d, J=6.3), 1.85˜1.94(3H, m),                               3.47(2H, brs), 4.04(1H, m), 4.15(4H, m),                                       6.30˜7.32(7H, m).                                   122     viscous liquid                                                                              NMR: 0.97(3H, d, J=7.0), 1.38(3H, d, J=7.0),                                   2.12(1H, m), 3.50(2H, brs),                                                    4.09˜4.35(5H, m), 6.33˜7.18(7H, m).           123     viscous liquid                                                                              NMR: 1.42(6H, s), 2.13(2H, s), 3.50(2H, brs),                                  4.00˜4.30(4H, m), 6.24˜7.14(7H, m).           124     viscous liquid                                                                              NMR: 0.92(3H, t, J=7.0), 1.34(3H, s), 1.70(2H, q,                              J=7.2), 2.01(1H, d, J=14.4),                                                   2.20(1H, d, J=14.4), 3.20(2H, brs),                                            4.00˜4.30(4H, m), 6.30˜7.44(7H, m).           125     viscoud liquid                                                         126     viscous liquid                                                                              NMR: 0.87(6H, t, J=7.2), 1.68(4H, q, J=7.2),                                   2.10(2H, s), 3.42(2H, brs),                                                    4.00˜4.30(4H, m), 6.22˜7.20(7H, m).           127     viscous liquid                                                                              NMR: 0.88(6H, t, J=7.2), 1.10˜1.50(2H, m),                               1.69(4H, q, J=7.2), 2.09(2H, s),                                               3.49(2H, brs), 3.90˜4.30(4H, m),                                         6.18˜7.10(7H, m).                                   128     viscous liquid                                                                              NMR: 1.36(3H, s), 1.62(3H, s), 1.68(1H, s), 1.80(3H,                           s), 3.54(2H, brs),                                                             6.20˜7.18(7H, m).                                   129     viscous liquid                                                                              NMR: 1.80˜2.24(6H, m), 3.06(1H, m), 3.53(3H,                             s), 3.55(2H, brs), 6.32˜7.22(7H, m).                130     viscous liquid                                                                              NMR: 1.40˜1.92(6H, m), 2.00˜2.30(2H, m),                           3.18(1H, m), 3.50(2H, brs), 3.76(3H, s),                                       6.18˜7.32(7H, m).                                   131     m.p. 140.0˜141.0                                                                      IR: 3385, 3320(ν.sub.NH), 3040(ν.sub.NH),                                1610, 1578, 1498, 1208, 1132, 1162, 990.                                       NMR: 1.31(3H, s), 1.47(3H, s), 1.60(3H, s), 1.82(1H,                           d, J=13.5), 2.04(1H, d, J=13.5),                                               3.12(2H, brs), 6.35(1H, d, J=2.7), 6.55(1H, dd,                                J=2.7, 9.0), 6.65(2H, d, J= 9.0),                                              6.89(2H, d, J=9.0), 7.20(1H, d, J=9.0).                   132     viscous liquid                                                                              NMR: 1.40(3H, d, J=7.2), 1.80(2H, m), 2.74(2H, m),                             3.48(2H, brs), 4.12(1H, m),                                                    6.60˜7.84(6H, m).                                   133     viscous liquid                                                                              NMR: 1.38(2H, d, J=7.2), 1.80(2H, m), 2.70(2H, m),                             3.52(2H, brs), 4.11(1H, m),                                                    6.52˜6.96(7H, m).                                   134     viscous liquid                                                                              NMR: 1.33(6H, s), 1.78(2H, t, J=7.2), 2.75(2H, t,                              J=7.2), 3.25(2H, brs),                                                         6.60˜7.80(6H, m).                                   135     viscous liquid                                                         136     viscous liquid                                                         137     viscous liquid                                                                              NMR: 1.55(3H, s), 1.66˜2.21(2H, m),                                      2.32˜3.10(2H, m), 3.22(2H, brs), 3.30(3H, s),                            6.50˜7.00(7H, m).                                   138     viscous liquid                                                                              NMR: 1.35(6H, d, J=6.9), 2.98˜3.10(1H, m),                               3.48(2H, brs), 6.36(1H, s),                                                    6.30˜7.32(7H, m).                                   139     viscous liquid                                                                              NMR: 0.98(3H, d, J=6.9), 1.02(3H, d, J=6.9),                                   1.90˜2.28(1H, m),                                                        2.64(2H, dd, J=2.7, 6.7), 3.47(2H, brs), 6.32(1H,                              s), 6.34˜7.18(7H, m).                               140     viscous liquid                                                                              NMR: 1.30(3H, t, J=7.7), 2.64(2H, q, J=7.7),                                   6.32˜7.34(8H, m).                                   141     viscous liquid                                                                              NMR: 0.80˜1.84(5H, m), 1.56(2H, t, J=7.7),                               3.50(2H, brs), 6.20˜7.40(8H, m).                    142     viscous liquid                                                                              NMR: 1.30(6H, d, J=6.7), 2.90˜3.14(1H, m),                               3.47(2H, brs), 6.20˜7.35(8H, m).                    143     viscous liquid                                                                              NMR: 1.42(3H, d, J=6.3), 2.84(1H, dd, J=7.2, 14.4),                            2.96(1H, dd, J=7.2, 14.4),                                                     3.56(2H, brs), 4.92(1H, m), 6.20˜7.60(6H, m).       144     viscous liquid                                                                              NMR: 1.48(3H, d, J=6.4), 2.88(1H, dd, J=7.7, 15.4),                            3.38(1H, dd, J=7.7, 15.4),                                                     3.52(2H, brs), 5.00(1H, m), 6.38˜7.32(8H, m).       146     viscous liquid                                                                              NMR: 1.26(6H, s), 1.80(2H, t, J=7.1), 2.82(2H, t,                              J=7.1), 3.52(2H, brs),                                                         6.33˜7.10(7H, m).                                   147     viscous liquid                                                         148     viscous liquid                                                                              NMR: 1.19(3H, d, J=7.2), 1.37(3H, s), 1.40(3H, s),                             2.24(3H, s), 3.10(1H, q, J=7.2),                                               3.48(2H, brs), 6.20˜7.20(6H, m).                    149     viscous liquid                                                                              NMR: 0.92(3H, t, J=7.2), 1.18(3H, d, J=6.3),                                   1.30(3H, s), 1.68(2H, q, J=7.2),                                               2.20(3H, s), 3.12(1H, q, J=6.3), 3.52(2H, brs),                                6.30˜7.22(6H, m).                                   150     viscous liquid                                                                              NMR: 1.30(3H, s), 1.82(2H, t, J=6.7), 2.16(3H, s),                             2.60(2H, t, J=6.7), 3.52(2H, brs),                                             6.20˜7.12(6H, m).                                   151     viscous liquid                                                         152     viscous liquid                                                                              NMR: 1.16(3H, d, J=7.2), 1.52(3H, s),                                          1.80˜2.12(1H, m), 2.22(3H, s),                                           2.44(2H, d, J=9.0), 3.24(3H, s), 3.48(2H, brs),                                6.24˜7.42(6H, m).                                   __________________________________________________________________________

The aromatic amine derivatives of the present invention are useful as intermediates for herbicides.

More particularly, compounds of general formula [IV]: ##STR192## wherein Ar and A are as defined above, and B is a hydrogen atom, a methyl or methoxy radical can be produced from the aromatic amine derivatives of the present invention by the method described in Japanese Patent Application No. 61-177858 (WO 87/00840) which is assigned to the same assignee as the present invention and whose disclosure is incorporated herein by reference. The compounds of formula [IV] are effective as herbicides as described in Japanese Patent Application No. 61-177858 (WO 87/00840). The specification of the Application reports the measured physical properties of the compounds, to which the measured physical properties of the aromatic amine derivatives of the present invention conform. 

We claim:
 1. The aromatic amine compound of the formula: ##STR193## wherein Ar is a radical selected from the group consisting of ##STR194## wherein R¹¹ to R¹⁵, R¹⁷ to R²⁰, R²⁷ -R²⁹ and R³⁵ to R³⁸ may be the same of different and are independently selected from the group consisting of hydrogen, lower alkyl radicals, and lower alkoxy radicals, R¹⁶ is selected from the group consisting of hydrogen, lower alkyl radicals, lower alkoxy radicals and hydroxyl, with the provisos that at least one of R¹¹ to R¹⁶ is a lower alkoxy radical or hydroxyl radical; R¹¹ and R¹⁵, or R¹⁵ and R¹⁶ may, taken together, represent an alkylene chain, which may be substituted with a lower alkyl radical, to form a 5- or 6-membered ring with the carbon atoms to which they are attached, R¹¹ and R¹² may, taken together, represent an ethylene dioxyl radical, or R¹⁴ or R¹⁵ may, taken together, represent a dichloromethylene radical; at least one of R¹⁷ to R²⁰ is a lower alkoxy radical; at least one of R²⁷ to R²⁹ is a lower alkoxy radical; and at least one of R³⁵ to R³⁸ is a lower alkoxy radical; and ##STR195## wherein X is selected from the group consisting of a hydrogen atom, a chlorine atom, and a trifluoromethyl radical.
 2. An aromatic amine as set forth in claim 1, wherein Ar is a group of the formula ##STR196## wherein R¹¹ to R¹⁶ are as defined.
 3. An aromatic amine according to claim 2, wherein X is a hydrogen atom.
 4. An aromatic amine according to claim 2, wherein X is a chlorine atom.
 5. An aromatic amine according to claim 2, wherein X is a trifluoromethyl radical.
 6. An aromatic amine as set forth in claim 1 wherein Ar is a group of the formula ##STR197## wherein R¹⁷ -R²⁰ are as defined.
 7. An aromatic amine according to claim 6, wherein X is a hydrogen atom.
 8. An aromatic amine according to claim 6, wherein X is a chlorine atom.
 9. An aromatic amine according to claim 6, wherein X is a trifluoromethyl radical.
 10. An aromatic amine as set forth in claim 1, wherein Ar is a group of the formula ##STR198## wherein R²⁷ -R²⁹ are as defined.
 11. An aromatic amine according to claim 10, wherein X is a hydrogen atom.
 12. An aromatic amine according to claim 10, wherein X is a chlorine atom.
 13. An aromatic amine according to claim 10, wherein X is a trifluoromethyl radical.
 14. An aromatic amine as set forth in claim 1, wherein Ar is a group of the formula ##STR199## wherein R³⁵ -R³⁸ are as defined.
 15. An aromatic amine according to claim 14, wherein x is a hydrogen atom.
 16. An aromatic amine according to claim 14, wherein x is a chlorine atom.
 17. An aromatic amine according to claim 14, wherein X is a trifluoromethyl radical.
 18. An aromatic amine as set forth in claim 3, wherein R¹¹ is hydrogen, methyl, ethyl or methoxy, R¹² is hydrogen or methyl or R¹¹ and R¹² together represent the group --O(CH₂)₂ O--, R¹³ is hydrogen or methyl, R¹⁴ is hydrogen, R¹⁵ is hydrogen or methyl, ethyl, i-propyl, methoxy or ethoxy or R¹⁴ and R¹⁵ together represent dichloromethylene, R¹⁶ is hydrogen or methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy or i-propoxy or R¹⁵ and R¹⁶ together represent pentamethylene.
 19. An aromatic amine as set forth in claim 4, wherein R¹¹ is hydrogen, methyl, ethyl or methoxy, R¹² is hydrogen or methyl or R¹¹ and R¹² together represent the group --O(CH₂)₂ O--, R¹³ is hydrogen or methyl, R¹⁴ is hydrogen, R¹⁵ is hydrogen or methyl, ethyl, i-propyl, methoxy or ethoxy or R¹⁴ and R¹⁵ together represent dichloromethylene, R¹⁶ is hydrogen or methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy or i-propoxy or R¹⁵ and R¹⁶ together represent pentamethylene.
 20. An aromatic amine as set forth in claim 5, wherein R¹¹ is hydrogen, methyl, ethyl or methoxy, R¹² is hydrogen or methyl or R¹¹ and R¹² together represent the group --O(CH₂)₂ O--, R¹³ is hydrogen or methyl, R¹⁴ is hydrogen, R¹⁵ is hydrogen or methyl, ethyl, i-propyl, methoxy or ethoxy or R¹⁴ and R¹⁵ together represent dichloromethylene, R¹⁶ is hydrogen or methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy or i-propoxy or R¹⁵ and R¹⁶ together represent pentamethylene.
 21. An amine compound as set forth in claim 7, wherein R¹⁷ is hydrogen or methyl, R¹⁸ is methoxy, R¹⁹ is hydrogen or methyl and R²⁰ is hydrogen or methyl.
 22. An amine compound as set forth in claim 8, wherein R¹⁷ is hydrogen or methyl, R¹⁸ is methoxy, R¹⁹ is hydrogen or methyl and R²⁰ is hydrogen or methyl.
 23. An amine compound as set forth in claim 9, wherein R¹⁷ is hydrogen or methyl, R¹⁸ is methoxy, R¹⁹ is hydrogen or methyl and R²⁰ is hydrogen or methyl.
 24. An aromatic amine as set forth in claim 15, wherein R³⁵ is hydrogen, R³⁶ is hydrogen or methyl, R³⁷ is methoxy and R³⁸ is methyl.
 25. An aromatic amine as set forth in claim 16, wherein R³⁵ is hydrogen, R³⁶ is hydrogen or methyl, R³⁷ is methoxy and R³⁸ is methyl.
 26. An aromatic amine as set forth in claim 17, wherein R³⁵ is hydrogen, R³⁶ is hydrogen or methyl, R³⁷ is methoxy and R³⁸ is methyl. 